Hydration of olefines



Patented July 30, 19 3 5 i A v .UNITED TATES PATENT OFFICE HYDBATION FOLEFINES No Drawing. Application December 22, 1933,

- Serial No. 703,673 g *1 Claims. (01.. 260-156) This invention relatesto the conversion of ole- Over 100 cc. of granules of this catalyst at270? lines into alcohols and has particular but not ex- 0. was passed asmixture of 3.4 mols. of ethylene elusive reference to the conversion ofethylene and 1 mol. of steam under a total pressure of 20 into ethylalcohol. atmospheres, and at a gas rate of approximately 5 Theconversion of ethylene into alcohol by ab- 400 litres per hour ofethylene calculated at nor- 5 sorption in strong sulphuric acid,dilution of the mal temperature and pressure. The hourly outethyl esterand distillation is known, as also is the put of ethyl alcohol was 6.69grams in the form direct combination of ethylene and steam under of a6.90 per cent. aqueous condensate. the catalytic influence of liquidsespecially sul- Example H 1o phuric acid and under the influence ofcertain 1 solid catalysts. v A mixture of 62.5 grams of CuCOa, 17.5grams One of the objects of the present invention is of 3:0: and 164.9grams of 90 per cent. phosphoric to provide an improved process ofconversion 0! acid (HaPOl) were heated down to dryness and oleflnes intoalcohols and particularly ethylene inbroken into pellets of pea-size.

to ethyl alcohol by means of steam in the Over 100 cc. of this catalystat 270 C. was 15 presence of solid catalysts. A further object is topassed a mixture f 3- m s. of yl a d 1- eflect the direct-conversion ofoleiines and steam mol. of steam under a total pressure of atmosinto thecorresponding alcohols, particularly e'thpheres at a gas rate ofapproximately 400 litres ylene and steam into ethyl alcohol, by the aidof of ethylene per hour (calculated at normal temcertain complexcatalysts containing boron. p atur a d pre su The h u y utp t f al- 0With the above objects in view the conversion cohol was 7.87 grams inthe form of 8.15 per' according to. the present invention is conductedat cent. condensate. The conversion of ethylene into elevatedtemperatures and preferably at moderethanol was 0.94 per cent. perpassage.

ately elevated pressure with the aid 01' a catalyst E 1 IH or catalystscontaining boron togetherlwith cop- 8 25 D iron manganese y w 01' ll f Acatalyst was prepared from 62.5 grams these, and phosphoric acid (HaPO4)in excess of CUCOJ, 86.2 grams MnCOa, 43.6 grams B20: and t t quired tofo m the o thophosphates of'the 464 grams of 90 per cent. Harm. Thesolid mass above mentioned elements pec y present. was baked at 200 C.for 2 hours and broken into The preferred method of operation is tocircugranules of pea-size. 30 latea mixture of the olefine and steamovera mass Over 100 cc. of this catalyst at 280 C. was of the catalystin, granular or tabletted :iorm passed a mixture of 3.0 mols. ofethylene and 1 p d 0 8 a tube and if desired pe ed in o mol. of steam ata total pressure of 20 atmoson inert material or in other knowncatalytic mapheres at a gas rate of about 400 litres per hour e fl ofethylene (calculated at normal temperature 35 The reaction maybe carriedout at temperatures and pressure). The hourly alcohol production rangingfrom 100 C. to 350 C. and at pressures was 9.11 grams in the form of an8.53 per cent. ranging from atmospheric up to about 250 atmosaqueouscondensate. pheres.

40 The following examples illustrate the manner of "Example W 40 acarrying the invention into eflect and the results A catalyst a preparedby evaporating down obtainedza mixture of MnCOs, B20: arid HaPO4 in theExample I molecular proportions of 1 mol. Mn0 0.5 mol. B203 and 2.8mols. phosphoric acid. About 3 per Ferrous oxalate, equivalent to 35.9grams of cent. of linseed oil was incorporated in the final 45 FeO, wasreacted with 191 grams of per cent. stages of the evaporation and theresulting mass phosphoric acid (H3PO4) and 17.4 grams of boron waspowdered, tabletted in ,4" tablets and finaltrioxide were added. Themass was finally baked ly baked at 200 C. for 2 hours. Over cc. of at-200 (Land broken into fragments of pea this catalyst at 275-290 C. waspassed a mix- 59 size. v ture of ethylene and steam under a total pres-50 sure of 20 atmospheres and ate. gas rate of about 400 litres ofethylene per hour calculated at normal temperature and pressure. Thefollowing table shows the influence of varying thesteamethylene ratioand the concentration of alcohol in the aqueous condensate and thehourly output of alcohol obtained.

Mols. 0! 01B per Hourly output of Percentage alcohol mol. oi H 0 C3H|OHgrams in condensate 3. 2 7. 66 6. 2. 7 8. 16 l 6. 32 2. 3 9. 05 5. 531.94 9. 98 5. 50 l. 65 10. 76 4. 83 l. 04 13.07 3. 47

Example V A catalyst or the composition 1 mol. MnO, 0.5 mol. B20: and3.6 mols. H3PO4 was prepared by evaporating down the requisitequantities of MnCOa, B203 and llaPOr and adding 5 per cent. of linseedoil in the final stage of evaporation. The mass was powdered, bakedat'250 C. for 2 hours and tabletted in A? pellets with addition of about3 per cent. linseed oil. The tablets were Example VI Over cc. of thecatalyst at 290 C. described in Example V was passed under a totalpressure oi! 40 atmospheres a mixture of 3 mols. of ethyl ene and 1 mol.of steam at a gas rate of about 1300 litres of ethylene per hour(calculated at normal temperature and pressure). The hourlyoutput ofalcohol was 48.0 grams in the form of a 11.48 per cent. aqueouscondensate.

Example VII Over 1000 cc. of the same catalyst as described in Example Vand spread on trays and at a temperature of 280-290 C. was passed amixture of 2.2 mols. ethylene and 1 mol. of steam under 20 atmospherespressure at a gas rate of about 10,-v

000 litres of ethylene per hour calculated at normal temperature andpressure. The hourly out put of alcohol was about grams in the form of a4.48 per cent. condensate.

Example VIII 92 grams of ferrous oxalate were evaporated with 284 gramsof phosphoric acid until all organic matter was destroyed. 57.5 grams ofmanganesecarbonate and 34.9 grams of boron trioxide were then added andthe whole was dried and baked. Over 100 cc. of this catalyst at atemperature of 270 C. and at a total pressure. of

20 atmospheres a mixture of ethylene and steam in the molecularproportions. of 3.7 mols. of ethylene to 1 mol. of steam was passed atthe rate,of 400 litres of ethylene per hour calculated at normaltemperature and pressure. The hourly output was 4.64 grams in the formof a 4.67 per cent. condensate.

The ethylene employed may be substantially pure or it may be merely acomponent of a mixture of gases.

What we claim is:- 1. The method of producing aliphatic .alcohols fromoleflnes comprising combining the oleflne with water vapour at elevatedtemperature in the presence of a solid catalyst comprising essentiallyphosphoric acid and boron together with any of the metals taken from thegroup consisting of iron, copper, manganese, the amount of phosphoricacid present in the catalyst being in excess of that required to formthe orthophosphates of the boron and of the group metal selected but notin so great an excess as to make the catalyst fluid.

2. The method of producing aliphatic alcohols from oleflnes comprisingcombining the olefine with water vapour at elevated temperature between100 C. and 350 C. and at super-atmospheric pressure up to about 250atmospheres in the presence of a solid catalyst comprising essentiallyphosphoric acid and boron together with any 01 the metals taken from thegroup consisting of iron, copper, manganese, the amount of phosphoricacid present in the catalyst being in excess of that required to formthe orthophosphates of the boron and of the group metal selected but notin so great an excess as to make the catalyst fluid.

3. The method of producing ethyl alcohol comprising combining ethylenewith water vapour at elevated temperature in the presence of a solidcatalyst comprising essentially phosphoric acid.

and boron together with any of-the metals taken from the groupconsisting of iron, copper, .manganese, the amount of phosphoric acidpresent in the catalyst being in excess of that required to form theorthophosphates of the boron and of the group metal selected but not inso great an excess as to make the catalyst fluid.

4. The method of producing ethyl alcohol comprising combining ethylenewith water vapour at elevated temperature between 100 C. and 350 C. inthe presence of a solid catalyst comprising essentially phosphoric acidand boron together with any of the metals taken'from the groupconsisting of iron, copper, manganese, the amount of phosphoric acidpresent in the catalyst being in excess of that required to form theorthophosphates of the boron and of the group metal selected but not inso great an excess as to make the catalyst fluid.

5. The method of producing ethyl alcohol comprising combining ethylenewith water vapour at elevated temperature and at super-atmosphericpressure up to about 250 atmospheres in the presence of a solid catalystcomprising essentially phosphoric acid and boron together with any ofthe metals taken from the group consisting of iron, copper, manganese,the amount of phosphoric acid present in the catalyst being in excess ofthat required to form the orthophos-' phates of the boron and of thegroup metal selected but not in so great an excess as to make thecatalyst fluid.

6. The method of producing ethyl alcohol comprising combining ethylenewith water vapour at elevated temperature between 100 C. and 350 C. andat super-atmospheric pressure up to about 250 atmospheres, in thepresence of a solid catalyst comprising essentially phosphoric acid andboron together with any of the metals taken from the group consisting ofiron, copper, manganese,

, the amount of phosphoric acid present in the catalyst being in excessof that required to form the orthophosphates oi' the boromand oiMillmbOfMflc new-urea V,

metal selected but not in so.great an excess a! cat in the catalystbeing in excess of that reto make the catalyst fluid. quired to form theorthte oi the boron 7. The method of producing ethyl alcohol colnand theorthophosphatee ot the two group metals prising combining ethylene withwater vapour at selected but not in so great an excess us to makeelevated temperature in the presence 01' a solid the catalyst fluid.

catalyst comprising essentially phosphoric acid WALTER PHILIP JOSHUA.

and boron together with any two 0! the metals T HUGGLII'ION STANLEY.taken from the group consisting of iron, copper. I JOHN BLAIR DYIIOCK.

